EP0309249B1 - Acryloyloxy- und Methacryloyloxy-Gruppen enthaltende Kondensations-Polymere - Google Patents

Acryloyloxy- und Methacryloyloxy-Gruppen enthaltende Kondensations-Polymere Download PDF

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Publication number
EP0309249B1
EP0309249B1 EP88308811A EP88308811A EP0309249B1 EP 0309249 B1 EP0309249 B1 EP 0309249B1 EP 88308811 A EP88308811 A EP 88308811A EP 88308811 A EP88308811 A EP 88308811A EP 0309249 B1 EP0309249 B1 EP 0309249B1
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groups
carbon atoms
diols
acryloyloxy
group
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EP0309249A3 (en
EP0309249A2 (de
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Gilbert C. C/O Minnesota Mining And Johnson
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3M Co
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Minnesota Mining and Manufacturing Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds

Definitions

  • This invention relates to linear ethylenically-unsaturated condensation polymers prepared from certain diols having pendent acrylate or methacrylate groups that are uncontaminated by the corresponding monols, triols, and polyols and compounds in which the unsaturated group is attached to a secondary carbon atom.
  • the invention specifically relates to condensation polymers containing acrylate and methacrylate groups which can provide products that can be embossed or polished and then cured to become chemically and abrasion resistant and to a process for preparing the acryloyloxy and methacryloyloxy group condensation polymers.
  • Such acryloyloxy and methacryloyloxy group-containing polyols have their hydroxyl groups located on secondary carbon atoms, introducing undesirable characteristics into polyurethanes prepared from them. Furthermore, acryloyloxy and methacryloyloxy group-containing polyols prepared from polyepoxides introduce a significant amount of residue from the body of the polyepoxide into polyurethanes prepared from them.
  • U.S.-A-3,210,327, 3,267,084, and 3,271,377 disclose monoacrylic and monomethacrylic esters of alkanediols having the formula wherein R is hydrogen or lower alkyl group, R1 is a lower alkyl group having 1 to 4 carbon atoms or hydrogen, and m is an integer of 1 to 4, inclusive. These esters are prepared by the hydrolysis of the corresponding ketal.
  • U.S.-A-4,578,504 discloses ethylenically-unsaturated diols having the formulae: wherein R is hydrogen or methyl. These esters are disclosed as useful in preparation of hydrogel coatings. There is no disclosure of their use in the preparation of acryloyloxy and methacryloyloxy group-containing polyurethanes.
  • U.S.-A-4,366,301 and 4,367,302 disclose acryloyloxy and methacryloyloxy group-containing polyurethanes prepared from an organic diisocyanate, a saturated linear diol, a diol having a molecular weight of less than 300, and an unsaturated diol having the formula wherein R is methyl or hydrogen and n is an integer between 1 and 4.
  • the unsatured diol used in preparing these polyurethanes has one hydroxyl group located on a secondary carbon atom. Such secondary hydroxy groups are often sluggish in condensation reactions and may lead to polyurethanes having undesirable characteristics.
  • acryloyloxy and methacryloyloxy group condensation polymers described in the prior art have been prepared from deficient acryloyloxy and methacryloyloxy group-containing diols that are contaminated by hydroxyl group-containing compounds having one and three or more hydroxyl groups, diols that have hydroxyl groups on secondary carbon atoms, or diols in which the acryloyloxy and methacryloyloxy group is attached to a secondary carbon atom.
  • the use of such deficient diols in condensation polymers considerably restricts possible processing methods and hence the possible use.
  • the present invention provides crosslinkable linear acryloyloxy and methacryloyloxy group-containing thermoplastic condensation polymers that are soluble in common organic solvents.
  • the condensation polymers of the invention comprise polyurethanes that are the reaction products of diisocyanates with specified acryloyloxy- or methacryloyloxyalkanediols, which diols are uncontaminated by the corresponding hydroxyl group-containing compounds having one and three or more hydroxyl groups and compounds in which the acryloyloxy and methacryloyloxy group is attached to a secondary carbon atom.
  • the end groups of the condensation polymers can be hydroxyl or isocyanate.
  • the solvent-soluble crosslinkable condensation polymers of the invention are represented by the general formula: wherein
  • the invention also provides a process for the preparation of crosslinkable, acryloyloxy- and methacryloyloxyalkyl pendent group-containing thermoplastic condensation polymers comprising the steps of:
  • the organic solvent soluble, crosslinkable, condensation polymers of the invention are useful in many applications because of the high concentration of acrylate or methacrylate groups that can be present. High concentration of these groups enables rapid crosslinking of the polymer under the influence of free radicals.
  • Solutions of the polymers can be applied to supports to form coatings that are hard and thermoplastic. The coatings can be embossed with various patterns such as decorative or information bearing patterns as are present in video discs and then cured to dimensionally stable articles.
  • the solutions can be applied to various substrates, e.g., wood, metal, plastic, or ceramic, to form coats that can then be shaped, ground, or polished and finally cured to chemical, solvent, and abrasion resistant coats.
  • Other applications in which the polymers are useful include adhesives, caulking and sealing compositions, elastomers, foams, casting and molding compositions, impregnating compositions, and binders.
  • high molecular weight condensation polymers can be made by the process of the invention. There is no termination of reacting chains to cause low molecular weights as is caused by monohydroxy group-containing compounds, nor is there crosslinking of polymer chains caused by tri and higher hydroxy group-containing compounds.
  • individual catenated groups means groups which are not directly linked to each other but are, rather, interspersed throughout the carbon chain.
  • the crosslinkable condensation polymers of the invention are prepared by the reaction, according to conventional procedures, of one or more organic diisocyanates with organic diols of which at least 5% by weight are specified acrylic or methacrylic ester substituted-1,3-propanediols, these diols being uncontaminated by the corresponding monols, triols, or higher polyols, to form the solvent-soluble crosslinkable acryloyloxy and methacryloyloxy group-containing polyurethanes.
  • the condensation polymer can be a polymer in which the acrylic or methacrylic ester unit is located randomly along its chain or the condensation polymer can be a block polymer having one or more of the polyurethane segments having acrylic or methacrylic units, and optionally one or more of polyether, polyester, polyolefin, and polysiloxane segments, each segment having a molecular weight of up to 15,000 or more, the acrylic or methacrylic ester unit being present in one or more of the polyurethane segments.
  • Diisocyanates that can be used in the preparation of the crosslinkable condensation polymers are well known and include any of the linear, branched, and cyclic aliphatic, aromatic and heterocyclic diisocyanates known in the polyurethane field.
  • preferred diiocyanates include 2,4-tolylene diisocyanate, 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane, bis-(4-isocyanatophenyl)methane, bis-(4-isocyanatocyclohexyl)methane, hexamethylene diisocyanate, 1,3-di(isocyanatoethyl)hydantoin, trimethylhexamethylene diisocyanate, and meta and para-tetramethylxylylene diisocyanate.
  • Diols that can be used in the preparation of the polyesters of the invention in addition to the specifically required ester substituted 1,3-propanediols have a number average molecular weight of 62 to about 15,000 and include saturated and unsaturated monomeric and polymeric diols.
  • monomeric diols include straight or branched chain alkylenediols having the formula HO(CH2) e OH in which e is an integer 2 to 10 and oxaalkylenediols having a formula H(OR5) f OH in which R5 is an alkylene group having 2 to 4 carbon atoms and f is a number having a value of 2 to 4.
  • Examples include ethyleneglycol, propyleneglycol 1,4-butanediol, 1,4-butenediol, neopentylglycol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethyleneglycol, and 1,11-(3,6-dioxa)undecanediol.
  • polymeric diols examples include poly(oxyalkylene)diols such as the Carbowax R diols available from Union Carbide, the poly(oxytetramethylene)diols such as Polymeg R diols available from Quaker Oats Company, and TerathaneTM diols from duPont, the polyester diols such as the Multron R poly(ethylene adipate)diols available from Mobay Chemical Co., the polycaprolactone diols such as the TONETM diols available from Union Carbide, the polyolefin diols such as the polyethylenediols available from Sartomer Co.
  • poly(oxyalkylene)diols such as the Carbowax R diols available from Union Carbide
  • poly(oxytetramethylene)diols such as Polymeg R diols available from Quaker Oats Company
  • Preferred substituted 1,3-propanediols are: 2,2-bis(acryloyloxymethyl)-1,3-propanediol 2,2-bis(methacryloyloxymethyl)-1,3-propanediol
  • Examples of other substituted 1,3-propanediols are: 2-acryloyloxymethyl-2-acetyloxymethyl-1,3-propanediol 2,-methacryloyloxymethyl-2-octadecanoyloxymethyl-1,3-propanediol
  • the polyurethanes of Formula I of the invention are prepared (step c) by the reaction of diisocyanates and diols of which at least 5 weight percent are acryloyloxy and methacryloyloxy group ester-substituted 1,3-propanediols of Formula III.
  • reaction can be generated as homopolymers, random copolymers, or block polymers through intermediate diol blocks or diisocyanate block. Since the 1,3-propanediols are readily polymerized through the acryloyloxy and methacryloyloxy group groups, it is preferable that the reaction be carried out at low temperatures, e.g. below about 100 C, preferably below 80 C, and in the presence of a free-radical inhibitor of polymerization such as 4-methoxyphenol. Preferably the reaction is carried out in the presence of 0.0001 to 0.5 percent by weight of reaction catalyst such as dibutyltin dilaureate based total weight of reactants.
  • reaction catalyst such as dibutyltin dilaureate based total weight of reactants.
  • the diols, 0.5 to 2.0 moles of diisocyanates per mole of diols, the polymerization inhibitor, the reaction catalyst and sufficient solvent, such as acetone and ethyl acetate, to provide a solution having about 10 to 75% solids are placed in a reactor equipped with an agitator and reflux condenser and the mixture agitated and heated until analysis indicates disappearance of the reagent used in less than the stoichiometric amount, generally 1 to 100 hours or more, preferably 1 to 10 hours.
  • the polyurethane can then isolated by removal of solvents by addition of the reaction mixture to a nonsolvent such as ethyl ether or by volatilization of the solvent. For many uses, the reaction mixture can be used without removal of solvent.
  • the molecular weight of the condensation polymers can be controlled by including in the polymerization mixture a monofunctional alcohol, carboxylic acid derivative such as halide, or isocyanate.
  • monofunctional compounds include but are not limited to pentanol, hexanol, cyclohexanol, octadecanol, 2-hydroxyethyl acrylate and methacrylate, acetyl chloride, stearoyl chloride, benzoyl chloride, isocyanatobenzene and 1-isocyanato-3- and 4-methylbenzene.
  • the polyurethanes of the invention are thermoplastic and, because of the pendent acrylate or methacrylate groups, articles of various shapes can be molded from compositions containing them and crosslinked to become insoluble and infusible.
  • a heat activated free-radical initiator is incorporated into the polyurethane compositions in an amount from 0.1 to 5.0 percent by weight of total weight of the composition.
  • heat activated free-radical initiators include but are not limited to benzoyl peroxide, lauroyl peroxide, dicyclohexyl percarbonate, and azo-bis(isobutyronitrile).
  • the free-radical initiated molded article can then be crosslinked (step d) by heating, preferably at a temperature between 50 and 150°.
  • Radiation activated free-radical initiators can be used in the composition, however they are not preferred when the molded article has a thickness greater than about 5 millimeters.
  • compositions suitable for coatings comprise a solution of from 5 to 50, perferably 10 to 30, percent by weight of the polyurethane in a suitable solvent and a heat or a radiation activated polymerization initiator.
  • condensation polymers of the invention can also be diluted with ethylenically-unsaturated materials (particularly acrylic acid and derivatives thereof and vinyl compounds) to modify or enhance their properties, e.g., hardness, flexibility, and adhesion to substrates.
  • ethylenically-unsaturated materials particularly acrylic acid and derivatives thereof and vinyl compounds
  • Both ethylenically-unsaturated low and high molecular weight materials can be used including for example methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, 2-chlorostyrene, 2,4-dichlorostyrene, acrylic acid, acrylamide, acrylonitrile, t-butyl acrylate, methyl acrylate, butyl acrylate, 2-(N-butylcarbamyl)ethyl methacrylate and 2-(N-ethylcarbamyl)-ethyl methacrylate.
  • modifying monomers that can be incorporated into the composition of the invention include 1,4-butylene dimethacrylate or diacrylate, ethylene dimethacrylate, hexanediol diacrylate or dimethacrylate, glyceryl diacrylate or dimethacrylate, glyceryl triacrylate or trimethacrylate, pentaerythritol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, diallyl phthalate, dipentaerythritol pentaacrylate, neopentylglycol diacrylate, and 1,3,5-tri(2-methacryloyloxyethyl)-s-triazine.
  • ethylenically-unsaturated coreactants can be blended with the condensation polymers of the invention.
  • coreactants include acrylated epoxy, acrylated urethane, and acrylated cellulose oligomers and resins.
  • modifying materials per part by weight of ethylenically- unsaturated condensation polymer can be used.
  • non-reactive film-forming resins such as nitrocellulose, can be added.
  • Heat and radiation activators of polymerization are well known.
  • the preferred initiators are the radiation activated initiators. Included among such initiators are acyloin and derivatives thereof, such as benzoin, benzoin methyl ether, benzoin ether ether, benzoin ispropyl ether, benzoin isobutyl ether, and 2-hydroxy-2-methyl-1,2-diphenylethanone; diketones such as benzil and diacetyl; phenones such as acetophenone, 2,2,2-tribromo-1-phenylethanone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2,2-tribromo-1-(2-nitrophenyl)-ethanone, benzophenone, 4,4'-bis(dimethylamino)-benzophenone and 1-hydroxycyclohexyl phenyl ketone.
  • acyloin and derivatives thereof such as benzoin, benzoin
  • the initiator is used in amounts ranging from 0.01 to 10% by weight of the total polymerization composition comprising polyester or the polyurethane.
  • the quantity is less than 0.01% by weight, the polymerization rate becomes extremely low. If the initiator is used in excess of about 10% by weight, no correspondingly improved affect can be expected. Thus, addition of such greater quantity is not economically justified and may detract from the properties of the cured coatings.
  • 0.25 to 5% of initiator is used in the polymerizable composition.
  • the photopolymerization of the compositions of the invention occurs on exposure of the compositions to any source of radiation emitting actinic radiation at a wavelength within the ultraviolet and visible spectral regions and by infrared radiation, i.e., thermal energy.
  • Suitable sources of radiation include mercury, xenon, carbon arc and tungsten filament lamps and sunlight.
  • Exposures may be from less than one second to ten minutes or more depending upon the amount of particular polymerizable materials, the photopolymerization catalyst being utilized, the radiation source, the distance of the composition from the source and the thickness of the coating to be cured.
  • the compositions may also be polymerized by exposure to electron beam irradiation. Generally speaking, the dosage necessary is from less than 1 megarad to 30 megarads or more.
  • An advantage of curing with electron beam irradiation is that highly pigmented compositions can be effectively cured at a faster rate than by mere exposure to actinic radiation.
  • the polyurethane compositions to be cured can also include other materials such as dyes; pigments, e.g., titanium dioxide, clay, calcium carbonate, and zinc chromate; glass and carbon fibers; glass beads and bubbles; organic polymers such as polyesters, polyurethanes, vinyl polymers, cellulose esters; and organic polymer fibers and particles.
  • additives may be present in quantities up to 500 parts or more per 100 parts polyurethane by weight and preferably from 0.01 to 200 parts on the same basis.
  • a solution containing 30% by weight of the polymer was prepared and 2% by weight based on dissolved solids of IrgacureTM 184, a photoinitiator available from Ciba-Geigy, was added.
  • the solution was coated using a MeyerTM bar at a dried thickness of about 25 micrometers on 100 micrometer thick polyester film and dried over night. A portion of the dried coating was cured in air and another under nitrogen in a RPCTM UV Processor (Radiation Processing Inc., subsidiary of Sumitomo Heavy Industries Ltd., Tokyo, Japan) having two lamps set on high using two passes at a belt speed of 25 centimeters per second.
  • Abrasion resistance of each was measured by abrading on a Taber Abraser (available from Pacific Scientific Co.) using 30 cycles with CS-17 wheels under a 500g load and quantified as percent haze (average of several samples) with a Hazegard hazemeter (available from Pacific Scientific Co.).
  • the sample cured in air showed a haze of 3.21 and the sample cured under nitrogen showed a haze of 2.48.
  • Triethylammonium chloride was filtered and the filtrate washed with cold water and a saturated solution of sodium sulfate. The washed filtrate was dried over anhydrous sodium sulfate and then filtered through silica gel. The solvent was then removed by evaporation under reduced pressure and the crude product, 2-phenyl-5,5-bis(acryloyloxymethyl)-1,3-dioxane, used in Step b directly or after recrystallization from ethyl acetate (m.p. 65°C).
  • the 2-phenyl-5,5-bis(hydroxymethyl)-1,3-dioxane used in Step a) was obtained by the reaction of benzaldehyde and pentaerythritol according to the procedure described in Org. Synthesis, Col. IV. p. 679 (1963).
  • Example 1 The procedure of Example 1 was followed by first drying by azeotropic distillation a mixture of 75.2 g 2,2-bis(acryloyloxymethyl)-1,3-propanediol (0.31 moles) 32.1 g neopentylglycol (0.31 moles) 0.09 g 4-methoxyphenol 250 ml ethyl acetate and then adding 103.6 g hexamethylene diisocyanate (0.62 moles) 0.12 ml DBTDL.
  • the polyurethane reaction product had a 1:1:2 mole ratio of unsaturated diol, neopentylglycol, and hexamethylene diisocyanate and a calculated acrylic ester equivalent weight of 260.
  • a solution of 7.5 g of the polyacrylated polyurethane of Example 1 and 7.5 g of the urethane acrylate oligomer Gafgard CDTM 238 (a polyester diol endcapped with diisocyanate and hydroxyethyl acrylate to yield a polymeric diacrylate available from GAF) was prepared in 35 g ethyl acetate (30% solids), 0.3 g of the photoinitiator IrgacureTM 184 (Ciba-Geigy) was added, and the blend coated, radiation cured in air, and evaluated as described in Example 1.
  • the abrasion resistance value of the cured blend was 6.58% haze after abrasion.
  • a solution of 7.5 g of the polyacrylated polyurethane oligomer of Example 8 and 7.5 g of the acrylated cellulosic polymer FX 911, available from 3M's Protective Chemical Division and described in U.S. Patent No. 4,565,857 was prepared in 35 g ethyl acetate (30% solids), 0.3 g of the photoinitiator IrgacureTM 184 was added, and the blend coated, cured in air, and evaluated as described in Example 1. The abrasion resistance value of the cured blend was 7.79% haze after abrasion.

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Claims (7)

  1. Kondensationspolymer mit dem Reaktionsprodukt von (1) Diolen, von denen mindestens eines ein Acryloyloxyalkandiol oder Methacryloxyalkandiol der Formel
    Figure imgb0029
     ist, in der R Wasserstoff oder Methyl ist, R³
    Figure imgb0030
     R⁴ Wasserstoff oder eine oder mehrere einwertige gesättigte lineare, verzweigte oder zyklische aliphatische Gruppen mit 1 bis 24 Kohlenstoffatomen oder aromatische Gruppen mit bis zu 18 Kohlenstoffatomen darstellt, wobei alle dieser Gruppen gegebenenfalls mit in Veresterungsreaktionen nicht reaktionsfähigen Gruppen substituiert sein können, das genannte Diol mit den entsprechenden hydroxylgruppenhaltigen Verbindungen mit einer, drei oder mehr Hydroxylgruppen und Verbindungen nicht verunreinigt ist, in denen die Acryloyloxy- und Methacryloyloxygruppe an einem sekundären Kohlenstoffatom angelagert ist und das Acryloyloxyalkandiol und Methacryloyloxyalkandiol in einer auf das Gesamtgewicht der vorhandenen genannten Diole bezogenen Menge im Bereich von 5 bis 100 Gew.-% vorhanden ist, und (2) einem organischen Diisocyanat, und das genannte Reaktionsprodukt ein lineares Polymer ist.
  2. Kondensationspolymer nach Anspruch 1, in dem das organische Diisocyanat ein aliphatisches, aromatisches oder heterozyklisches Diisocyanat ist.
  3. Kondensationspolymer nach Anspruch 1 oder 2, das die Formel
    Figure imgb0031
     hat, in der
    W und Z   endständige Gruppen sind
    R¹   eine oder mehrere zweiwertige organische Gruppen darstellt,
    Y   -NH- ist
    a   eine Zahl mit einem Wert von 2 bis 200 ist,
    R²   mindestens eine zweiwertige organische Gruppe darstellt, die der gesättigte oder ungesättigte Rest ist, der verbleibt, wenn zwei Hydroxylgruppen von 1) einem polymeren Diol, das aus den Polyetherdiolen, Polyesterdiolen, Polyolefindiolen, Polyamiddiolen, Polyurethandiolen und Polysiloxandiolen mit einem Molekulargewicht bis zu 15 000 ausgewählt ist, 2) einem monomeren Diol, das ein lineares, verzweigtes oder zyklisches aliphatisches Diol mit 2 bis 12 Kohlenstoffatomen ist, 3) einem Aryl oder Alkaryldiol mit 6 bis 15 Kohlenstoffatomen oder 4) mindestens einem 1,3-Propandiol der Formel
    Figure imgb0032
     abgespalten wird, in der R³
    Figure imgb0033
    R⁴   Wasserstoff und/oder einwertige gesättigte oder ungesättigte lineare, verzweigte oder zyklische aliphatische Gruppen mit 1 bis 24 Kohlenstoffatomen oder aromatische Gruppen mit 6 bis 18 Kohlenstoffatomen darstellt, von welchen Gruppen alle gegebenenfalls mit in Veresterungsreaktionen nicht reaktionsfähigen Gruppen substituiert sein können,
    wobei mindestens 5 Gew.-% aller Diole aus einem 1,3-Propandiol der Formel II bestehen, in der R⁴ -CH=CH₂ oder
    Figure imgb0034
     ist, das genannte Diol mit den entsprechenden hydroxylgruppenhaltigen Verbindungen mit einer drei oder mehr Hydroxylgruppen und Verbindungen nicht verunreinigt ist, in denen die Acryloyloxy- und Methacryloyloxygruppe an einem sekundären Kohlenstoffatom angelagert ist und das Kondensationsprodukt ein lineares Polymer ist.
  4. Kondensationspolymer nach Anspruch 3, in dem R¹ eine zweiwertige aliphatische Gruppe mit 2 bis 40 Kohlenstoffatomen oder eine zweiwertige aromatische Gruppe mit 5 bis 24 Kohlenstoffatomen ist und R¹ gegebenenfalls mit nichtstörenden Gruppen substituiert ist, die aus einzeln verketteten -O-;
    Figure imgb0035
     ausgewählt sind, wobei R¹⁰ ein niederes Alkyl mit 3 bis 4 Kohlenstoffatomen ist.
  5. Stoffzusammensetzung mit dem Kondensationspolymer nach Anspruch 3 und 4 und einer wenigstens eine acryloyloxy- oder methacryloyloxygruppe enthaltenden Verbindung.
  6. Vernetztes Kondensationspolymer nach Anspruch 1 bis 5.
  7. Verfahren zum Erzeugen eines acryloyloxy- oder methacryloyloxygruppen enthaltenden linearen Kondensationspolymers nach Anspruch 1 bis 4 mit folgenden Schritten:
    a) es wird ein Polymerisationsgemisch hergestellt, das aus
    1) einem oder mehreren organischen Diisocyanaten und
    2) einem oder mehreren polymeren und monomeren Diolen besteht, von denen 5 bis 100 Gew.-% Diole sind, die durch die Formel
    Figure imgb0036
     dargestellt sind, in der
    R   Wasserstoff oder Methyl ist,
    R³   
    Figure imgb0037
     ist und
    R⁴   Wasserstoff oder eine oder mehrere einwertige gesättigte lineare, verzweigte oder zyklische aliphatische Gruppen mit 1 bis 24 Kohlenstoffatomen darstellt, wobei alle dieser Gruppen gegebenenfalls mit in Veresterungsreaktionen nicht reaktionsfähigen Gruppen substituiert sein können, das genannte Diol mit den entsprechenden hydroxylgruppenhaltigen Verbindungen mit einer, drei oder mehr Hydroxylgruppen und Verbindungen nicht verunreinigt ist, in denen die Acryloyloxy- und Methacryloyloxygruppe an einem sekundären Kohlenstoffatom angelagert ist
    und gegebenenfalls einer das Molekulargewicht beeinflussenden Menge eines einfunktionellen Alkohols oder organischen Isocyanats und gegebenenfalls einer wirksamen Menge eines wärme- oder strahlungsaktivierbaren Polymerisationsinitiators, eines organischen Lösungsmittels, eines Katalysators, eines Farbstoffes, eines Pigments, eines Füllstoffes, eines Teilchens und/oder eines organischen Polymers,
    b) das Polymerisationsgemisch wird bei einer wirksamen Temperatur während einer Zeit erhitzt, die zum Herbeiführen einer Polymerisation genügt.
EP88308811A 1987-09-22 1988-09-22 Acryloyloxy- und Methacryloyloxy-Gruppen enthaltende Kondensations-Polymere Expired - Lifetime EP0309249B1 (de)

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US99612 1987-09-22
US07/099,612 US4910281A (en) 1987-09-22 1987-09-22 Acryloyloxy and methacryloyloxy group-containing condensation polymers

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EP0309249A2 EP0309249A2 (de) 1989-03-29
EP0309249A3 EP0309249A3 (en) 1990-04-18
EP0309249B1 true EP0309249B1 (de) 1993-11-24

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JP5797981B2 (ja) * 2011-09-06 2015-10-21 東洋ゴム工業株式会社 研磨パッド
JP5875300B2 (ja) * 2011-09-06 2016-03-02 東洋ゴム工業株式会社 研磨パッド及びその製造方法
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US4910281A (en) 1990-03-20
EP0309249A3 (en) 1990-04-18
EP0309249A2 (de) 1989-03-29
JPH01108215A (ja) 1989-04-25
CA1333836C (en) 1995-01-03
ES2059529T3 (es) 1994-11-16
DE3885837D1 (de) 1994-01-05
DE3885837T2 (de) 1994-05-26

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